JP5219952B2 - Copper foil for lithium-ion battery current collector - Google Patents
Copper foil for lithium-ion battery current collector Download PDFInfo
- Publication number
- JP5219952B2 JP5219952B2 JP2009169269A JP2009169269A JP5219952B2 JP 5219952 B2 JP5219952 B2 JP 5219952B2 JP 2009169269 A JP2009169269 A JP 2009169269A JP 2009169269 A JP2009169269 A JP 2009169269A JP 5219952 B2 JP5219952 B2 JP 5219952B2
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- silane coupling
- current collector
- coupling agent
- organic film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 192
- 239000011889 copper foil Substances 0.000 title claims description 167
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 58
- 238000010168 coupling process Methods 0.000 claims description 27
- 229910000077 silane Inorganic materials 0.000 claims description 27
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- 230000008878 coupling Effects 0.000 claims description 23
- 238000005859 coupling reaction Methods 0.000 claims description 23
- 230000003746 surface roughness Effects 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 33
- 230000002265 prevention Effects 0.000 description 33
- 239000011149 active material Substances 0.000 description 20
- -1 by dipping Substances 0.000 description 14
- 238000003466 welding Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000010731 rolling oil Substances 0.000 description 6
- 238000007788 roughening Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- ZDSFBVVBFMKMRF-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)silane Chemical compound C=CC[Si](C)(C)CC=C ZDSFBVVBFMKMRF-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- LNRDORCPMGMXIT-UHFFFAOYSA-N n'-[(4-ethenylphenyl)methyl]-n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCN(CCN)CC1=CC=C(C=C)C=C1 LNRDORCPMGMXIT-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000004439 roughness measurement Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
Description
本発明はリチウムイオン電池集電体用銅箔に関し、とりわけリチウムイオン二次電池負極集電体用銅箔に関する。 The present invention relates to a copper foil for a lithium ion battery current collector, and more particularly to a copper foil for a lithium ion secondary battery negative electrode current collector.
リチウムイオン電池はエネルギー密度が高く、比較的高い電圧が得ることができるという特徴を有し、ノートパソコン、ビデオカメラ、デジタルカメラ、携帯電話等の小型電子機器用に多用されている。将来、電気自動車や一般家庭の分散配置型電源といった大型機器の電源としての利用も有望視されている。 Lithium ion batteries have a feature of high energy density and a relatively high voltage, and are widely used for small electronic devices such as notebook computers, video cameras, digital cameras, and mobile phones. In the future, it is expected to be used as a power source for large equipment such as electric vehicles and distributed power sources for general households.
リチウムイオン電池の電極体は一般に、正極１１、セパレータ１２及び負極１３が幾十にも巻回又は積層されたスタック構造を有している。図１は、リチウムイオン電池のスタック構造の模式図である。典型的には、正極は、アルミニウム箔でできた正極集電体とその表面に設けられたＬｉＣｏＯ2、ＬｉＮｉＯ2及びＬｉＭｎ2Ｏ4といったリチウム複合酸化物を材料とする正極活物質から構成され、負極は銅箔でできた負極集電体とその表面に設けられたカーボン等を材料とする負極活物質から構成される。正極同士及び負極同士は各タブ（１４、１５）でそれぞれ溶接される。また、正極及び負極はアルミニウムやニッケル製のタブ端子と接続されるが、これも溶接により行われる。溶接は超音波溶接により行われるのが通常である。 An electrode body of a lithium ion battery generally has a stack structure in which a positive electrode 11, a separator 12, and a negative electrode 13 are wound or stacked in dozens. FIG. 1 is a schematic diagram of a stack structure of a lithium ion battery. Typically, the positive electrode is composed of a positive electrode current collector made of aluminum foil and a positive electrode active material made of a lithium composite oxide such as LiCoO 2 , LiNiO 2 and LiMn 2 O 4 provided on the surface thereof, The negative electrode is composed of a negative electrode current collector made of copper foil and a negative electrode active material made of carbon or the like provided on the negative electrode current collector. The positive electrodes and the negative electrodes are welded by the tabs (14, 15), respectively. Moreover, although a positive electrode and a negative electrode are connected with the tab terminal made from aluminum or nickel, this is also performed by welding. The welding is usually performed by ultrasonic welding.
負極の集電体として使用される銅箔に要求される特性としては、負極活物質との密着性、銅箔又はタブ端子との超音波溶接性、更には防錆性が挙げられる。 Properties required for the copper foil used as the current collector for the negative electrode include adhesion with the negative electrode active material, ultrasonic weldability with the copper foil or tab terminal, and rust prevention.
活物質層との密着性を改善するための一般的な方法としては、予め粗化処理と呼ばれる銅箔表面に凹凸を形成する表面処理が挙げられる。粗化処理の方法としては、ブラスト処理、粗面ロールによる圧延、機械研磨、電解研磨、化学研磨及び電着粒のめっき等の方法が知られており、これらの中でも特に電着粒のめっきは多用されている。この技術は、硫酸銅酸性めっき浴を用いて、銅箔表面に樹枝状又は小球状に銅を多数電着せしめて微細な凹凸を形成し、投錨効果による密着性の改善を狙ったり、体積変化の大きな活物質の膨張時に活物質層の凹部に応力を集中させて亀裂を形成せしめ、集電体界面に応力が集中することによる剥離を防ぐことを狙ったりして行われている（例えば、特許第３７３３０６７号公報）。 As a general method for improving the adhesion with the active material layer, a surface treatment for forming irregularities on the surface of the copper foil, which is called a roughening treatment, can be mentioned. As the method of roughening treatment, methods such as blasting, rolling with a rough surface roll, mechanical polishing, electrolytic polishing, chemical polishing, and plating of electrodeposited grains are known, and among these, electrodeposited grain plating is particularly preferred. It is used a lot. This technology uses a copper sulfate acidic plating bath to deposit a large number of copper in a dendritic or small spherical shape on the surface of the copper foil to form fine irregularities, aiming to improve adhesion by the anchoring effect, or volume change It is carried out with the aim of preventing peeling due to stress concentration at the current collector interface by concentrating stress on the concave portion of the active material layer during expansion of the large active material to form a crack (for example, Japanese Patent No. 3733067).
特許第３７３３０６５号公報には、好ましい表面性状が粗さのパラメータで具体的に特定されており、表面粗さＲａの値が大きな銅箔を集電体として用いることにより、集電体と活物質との密着性が向上することが記載されている（段落０２０９）。集電体の表面粗さＲａは、０．０１μｍ以上であることが好ましく、さらに好ましくは０．０１〜１μｍであり、さらに好ましくは０．０５〜０．５μｍであるとされる（段落００２１等）。集電体の表面粗さＲａと局部山頂の平均間隔Ｓは、１００Ｒａ≧Ｓの関係を有することが好ましいとされる（段落００２２等）。集電体表面の凹凸の凸部の形状は錐体状であることが好ましいとされる（段落００２３等）。
そして、このような表面形態は、電解銅箔（段落００４４）、圧延銅箔の表面に電解法により銅を析出させて表面を粗面化すること（段落００４５）、及びエメリー紙で研磨処理すること（段落０２０５）で得られることが記載されている。
In Japanese Patent No. 3733065, a preferable surface property is specifically specified by a roughness parameter, and a current collector and an active material are obtained by using a copper foil having a large surface roughness Ra as a current collector. It is described that the adhesiveness to the surface is improved (paragraph 0209). The surface roughness Ra of the current collector is preferably 0.01 μm or more, more preferably 0.01 to 1 μm, and further preferably 0.05 to 0.5 μm (paragraph 0021 and the like). ). The surface roughness Ra of the current collector and the average interval S between the local peaks are preferably 100Ra ≧ S (paragraph 0022 and the like). The shape of the convex and concave portions on the surface of the current collector is preferably a cone (paragraph 0023 and the like).
Such surface morphology is obtained by electrolytic copper foil (paragraph 0044), precipitation of copper on the surface of the rolled copper foil by an electrolytic method to roughen the surface (paragraph 0045), and polishing with emery paper. (Paragraph 0205).
防錆性を向上させる方法としては、銅箔表面をクロメート処理やシランカップリング処理する方法が知られている。シランカップリング処理は、密着性の向上効果も得られる。例えば、特開２００８−１８４６５７号公報には、銅箔の少なくとも一方の面に、ニッケル、コバルト、タングステン、モリブデンのうち少なくとも一つ以上から選択された金属又はこれら金属とメタロイド金属であるリン又は、ほう素との間で形成されたバリア層を形成し、次いで形成したバリア層上に三価クロムをクロム源とするクロメート処理を施し、得られた三価クロメート皮膜上にシランカップリング処理を施すことで、密着性及び防錆性が向上したことが記載されている。ここには、シランカップリング処理の条件として、シランカップリング剤の濃度を０．５ｍＬ／Ｌ以上、１０ｍＬ／Ｌ以下とすること、液温３０℃で５秒間浸漬後、直ちに処理液から取り出して乾燥させることが記載されている。 As a method for improving rust prevention, a method of chromate treatment or silane coupling treatment on the surface of copper foil is known. Silane coupling treatment can also improve adhesion. For example, in Japanese Patent Application Laid-Open No. 2008-184657, at least one surface of a copper foil is a metal selected from at least one of nickel, cobalt, tungsten, and molybdenum, or phosphorus that is a metalloid metal and these metals, A barrier layer formed with boron is formed, then a chromate treatment using trivalent chromium as a chromium source is performed on the formed barrier layer, and a silane coupling treatment is performed on the obtained trivalent chromate film Thus, it is described that adhesion and rust prevention properties are improved. Here, as conditions for the silane coupling treatment, the concentration of the silane coupling agent should be 0.5 mL / L or more and 10 mL / L or less, immersed for 5 seconds at a liquid temperature of 30 ° C., and then immediately removed from the treatment liquid. It is described to be dried.
一方、超音波溶接性については、従来、材料の溶接性に合わせて溶接エネルギーを大きく与えることで大きな問題とはなっていなかった。しかながら、溶接エネルギーを大きく与えることは溶接に使われる消耗品の消耗が激しいことから、近年のコスト削減において溶接エネルギーを小さくしても溶接性のよい銅箔が求められるようになってきた。超音波溶接性と防錆性の両立を図る方法としては、超音波溶接性（接合強度）が銅箔表面に設けた防錆処理層の厚さと銅箔の表面粗さに大きく影響されることに着目して、クロム水和酸化物層の銅箔表面への被覆量を０．５〜７０μｇ−Ｃｒ／ｄｍ2に規定したり、クロム水和酸化物層が被覆されている面のＲｚ（ＪＩＳＢ０６０１−１９９４で規定する１０点平均粗さ）を２．０μｍ以下にしたりする方法が特開２００９−６８０４２号公報に記載されている。実施例にはこのような表面粗さを電解銅箔で作り込んだことが記載されている。 On the other hand, with regard to ultrasonic weldability, hitherto, it has not been a big problem by giving large welding energy in accordance with the weldability of materials. However, giving a large amount of welding energy consumes a lot of consumables used for welding. Therefore, in recent cost reduction, a copper foil having good weldability has been demanded even if the welding energy is reduced. As a method to achieve both ultrasonic weldability and rust prevention, the ultrasonic weldability (joint strength) is greatly affected by the thickness of the rust-proofing layer provided on the copper foil surface and the surface roughness of the copper foil. Paying attention to the above, the coating amount of the chromium hydrated oxide layer on the surface of the copper foil is regulated to 0.5 to 70 μg-Cr / dm 2 , or the surface of the surface coated with the chromium hydrated oxide layer is Rz ( Japanese Unexamined Patent Application Publication No. 2009-68042 discloses a method of reducing the 10-point average roughness defined in JIS B0601-1994) to 2.0 μm or less. In the examples, it is described that such surface roughness is made of electrolytic copper foil.
このように、リチウムイオン電池の集電体として使用される銅箔の特性向上のための技術開発が、密着性及び防錆性については種々行われてきているが、超音波溶接性については少なく、いずれも密着性、超音波溶接性、及び防錆性のすべてには着目しておらず、これら三種類の特性をバランス良く向上させる方法は未だ知られていない。そこで、本発明はこれら三種類の特性をバランス良く向上したリチウムイオン電池の集電体用銅箔を提供することを第一の課題とする。本発明はそのような銅箔を製造する方法を提供することを第二の課題とする。更に、本発明は本発明に係る銅箔を集電体として用いたリチウムイオン電池を提供することを第三の課題とする。 As described above, various technical developments for improving the characteristics of copper foil used as a current collector of a lithium ion battery have been conducted for adhesion and rust prevention, but there is little for ultrasonic weldability. None of them pay attention to all of adhesion, ultrasonic weldability, and rust prevention, and a method for improving these three properties in a well-balanced manner is not yet known. In view of this, the first object of the present invention is to provide a copper foil for a current collector of a lithium ion battery in which these three types of characteristics are improved in a well-balanced manner. This invention makes it the 2nd subject to provide the method of manufacturing such copper foil. Furthermore, this invention makes it a 3rd subject to provide the lithium ion battery which used the copper foil which concerns on this invention as a collector.
本発明者は上記課題を解決するために研究を重ねたところ、シランカップリング処理に課題解決の糸口を見出した。そこで、シランカップリング処理の条件を詳細に検討したところ、銅箔表面をシランカップリング処理することによって得られる有機皮膜の厚みを従来よりも薄くすることで、好ましくは、更に銅箔表面に残存する未反応のシランカップリング剤を低減することで、密着性、銅箔又はタブ端子との超音波溶接性、防錆性のバランスにより優れた銅箔を提供できることを見出した。 The present inventor conducted research to solve the above-mentioned problems, and found a clue to solve the problems in the silane coupling treatment. Therefore, when the conditions of the silane coupling treatment were examined in detail, the thickness of the organic film obtained by performing the silane coupling treatment on the copper foil surface was made thinner than before, and preferably remained on the copper foil surface. It has been found that by reducing the amount of unreacted silane coupling agent, an excellent copper foil can be provided by a balance of adhesion, ultrasonic weldability with copper foil or tab terminal, and rust prevention.
以上の知見を基礎として完成した本発明は一側面において、表面の少なくとも一部がシランカップリング処理されたリチウムイオン電池集電体用銅箔であって、ＸＰＳによる深さ方向分析でＳｉを検出し、かつＣ検出量がバックグラウンドレベルよりも大きい深さ範囲（以下、「有機皮膜厚み」という。）の平均値Ｄ0が１．０〜５．０ｎｍであり、且つ表面粗さが０．０１μｍ≦Ｒａ≦０．１０μｍを満たすリチウムイオン電池集電体用銅箔である。 The present invention completed on the basis of the above knowledge is, in one aspect, a copper foil for a lithium ion battery current collector in which at least a part of the surface is subjected to silane coupling treatment, and detects Si by XPS depth analysis. and, and a large depth range C detection amount than the background level (hereinafter. referred to as "organic film thickness") Ri average D 0 is 1.0~5.0nm der of the and the surface roughness 0 It is a copper foil for a lithium ion battery current collector that satisfies .01 μm ≦ Ra ≦ 0.10 μm .
本発明に係る銅箔は一実施形態において、純水に１０秒間浸漬する洗浄操作後の有機皮膜厚みの平均値Ｄ1が１．０ｎｍ以上である。 In one embodiment, the copper foil according to the present invention has an average value D 1 of an organic film thickness after a cleaning operation of immersing in pure water for 10 seconds is 1.0 nm or more.
本発明に係る銅箔は別の一実施形態において、洗浄操作前の有機皮膜厚みの平均値Ｄ0に対する、純水に１０秒間浸漬する洗浄操作後の有機皮膜厚みの平均値Ｄ1の比率（Ｄ1／Ｄ0）が０．６以上である。 In another embodiment of the copper foil according to the present invention, the ratio of the average value D 1 of the organic film thickness after the cleaning operation immersed in pure water for 10 seconds to the average value D 0 of the organic film thickness before the cleaning operation ( D 1 / D 0) is 0.6 or more.
本発明に係る銅箔は更に別の一実施形態において、銅箔が電解銅箔であり、Ｓ面、Ｍ面における表面粗さについて、どちらの面も０．０１μｍ≦Ｒａ≦０．１０μｍを満たす。 In yet another embodiment of the copper foil according to the present invention, the copper foil is an electrolytic copper foil, and both surfaces satisfy 0.01 μm ≦ Ra ≦ 0.10 μm with respect to the surface roughness on the S surface and the M surface. .
本発明に係る銅箔は更に別の一実施形態において、銅箔が圧延銅箔であり、上下面の圧延平行方向における表面粗さについて、どちらの面もＲＳｍ≦２０μｍを満たし、且つ、ＲＳｍ／Ｒａ≦４００である。 In yet another embodiment of the copper foil according to the present invention, the copper foil is a rolled copper foil, and the surface roughness in the rolling parallel direction of the upper and lower surfaces, both surfaces satisfy RSm ≦ 20 μm, and RSm / Ra ≦ 400.
本発明に係る銅箔は更に別の一実施形態において、リチウムイオン二次電池負極集電体用である。 In yet another embodiment, the copper foil according to the present invention is for a negative electrode current collector of a lithium ion secondary battery.
本発明は別の一側面において、本発明に係る銅箔を集電体として用いたリチウムイオン電池である。 In another aspect, the present invention is a lithium ion battery using the copper foil according to the present invention as a current collector.
本発明は更に別の一側面において、銅箔表面の少なくとも一部を０．１〜１．０質量％のシランカップリング剤溶液と接触させる工程と、次いでシランカップリング剤を銅箔表面の銅と反応させる工程とを含み、前記反応は５０℃以上の雰囲気中で加熱処理を行うことで実施し、これによりＸＰＳによる深さ方向分析でＳｉを検出し、かつＣ検出量がバックグラウンドレベルよりも大きい深さ範囲（以下、「有機皮膜厚み」という。）の平均値Ｄ 0 が１．０〜５．０ｎｍであり、且つ表面粗さが０．０１μｍ≦Ｒａ≦０．１０μｍを満たす銅箔を製造するリチウムイオン電池集電体用銅箔の製造方法である。
In yet another aspect of the present invention, the step of bringing at least a part of the surface of the copper foil into contact with a 0.1 to 1.0 mass% silane coupling agent solution, and then the silane coupling agent on the copper foil surface copper The reaction is carried out by performing heat treatment in an atmosphere of 50 ° C. or higher , whereby Si is detected by XPS depth direction analysis, and the C detection amount is lower than the background level. Copper foil having an average value D 0 of 1.0 to 5.0 nm and a surface roughness of 0.01 μm ≦ Ra ≦ 0.10 μm in a large depth range (hereinafter referred to as “organic film thickness”) Is a method for producing a copper foil for a lithium ion battery current collector.
本発明に係るリチウムイオン電池集電体用銅箔の製造方法は一実施形態において、未反応のシランカップリング剤を銅箔表面から除去する工程を更に含む。 In one embodiment, the method for producing a copper foil for a lithium ion battery current collector according to the present invention further includes a step of removing the unreacted silane coupling agent from the surface of the copper foil.
本発明に係る銅箔は負極活物質との密着性、銅箔又はタブ端子との超音波溶接性、更には防錆性がバランス良く向上する。そのため、リチウムイオン電池の集電体として好適に使用することができる。 The copper foil according to the present invention improves the adhesion with the negative electrode active material, the ultrasonic weldability with the copper foil or the tab terminal, and further the rust prevention with a good balance. Therefore, it can be suitably used as a current collector for a lithium ion battery.
１．銅箔基材
本発明において、銅箔は電解銅箔及び圧延銅箔のいずれでもよい。また、「銅箔」には銅合金箔も含まれるものとする。銅箔の材料としては、特に制限はなく、用途や要求特性に応じて適宜選択すればよい。例えば、限定的ではないが、圧延銅箔の場合、高純度の銅（無酸素銅やタフピッチ銅等）の他、Ｓｎ入り銅、Ａｇ入り銅、Ｎｉ、Ｓｉ等を添加したＣｕ−Ｎｉ−Ｓｉ系銅合金、Ｃｒ、Ｚｒ等を添加したＣｕ−Ｃｒ−Ｚｒ系銅合金のような銅合金が挙げられる。
1. Copper foil base material In this invention, any of an electrolytic copper foil and a rolled copper foil may be sufficient as copper foil. The “copper foil” includes a copper alloy foil. There is no restriction | limiting in particular as a material of copper foil, What is necessary is just to select suitably according to a use or a required characteristic. For example, although not limited, in the case of a rolled copper foil, Cu-Ni-Si added with Sn-containing copper, Ag-containing copper, Ni, Si, etc., in addition to high-purity copper (oxygen-free copper, tough pitch copper, etc.) And copper alloys such as Cu-Cr-Zr-based copper alloys to which Cr-based copper alloys, Cr, Zr and the like are added.
電解銅箔と比べた圧延銅箔の利点について説明する。リチウムイオン電池の集電体として使用する場合、銅箔を薄肉化した方がより高容量の電池を得ることができるが、薄肉化すると強度低下による破断の危険性が生じる。この点、電解銅箔よりも強度の高い圧延銅箔を使用するのが有利となる。圧延銅箔は振動が継続的に発生する環境等に対応し、耐屈曲性が高い点でも優れている。 The advantage of the rolled copper foil compared with the electrolytic copper foil will be described. When used as a current collector for a lithium ion battery, it is possible to obtain a battery having a higher capacity by reducing the thickness of the copper foil. However, if the thickness is reduced, there is a risk of breakage due to a decrease in strength. In this respect, it is advantageous to use a rolled copper foil having higher strength than the electrolytic copper foil. The rolled copper foil is excellent in that it has high bending resistance in response to an environment in which vibration continuously occurs.
また、電解銅箔では製造工程の都合上、陰極に接していた側の平滑で光沢があるＳ面と、これとは反対側の粗く無光沢であるＭ面が生じる。両者は表面性状は通常異なっているが、電解条件の管理によっては、平滑、かつ両面の差異がほとんどなくなるように製造することが可能である。ただし、このような制御は、添加剤や電解条件管理に多大なノウハウを必要とする。一方、圧延銅箔では、その製造プロセスにおいて、原理的に、平滑な両面を得るのに適しており、実質的に同一の表面性状とすることができるので有利である。 Moreover, in the electrolytic copper foil, a smooth and glossy S surface on the side in contact with the cathode and a rough and matte M surface on the opposite side are produced due to the manufacturing process. Both have different surface properties, but depending on the control of the electrolysis conditions, they can be manufactured to be smooth and have almost no difference between both surfaces. However, such control requires a great deal of know-how in managing additives and electrolytic conditions. On the other hand, in the rolled copper foil, in the manufacturing process, in principle, it is suitable for obtaining smooth both sides, and it is advantageous because it can have substantially the same surface properties.
銅箔の厚みは特に制限はなく、要求特性に応じて適宜選択すればよい。一般的には１〜１００μｍであるが、リチウム二次電池負極の集電体として使用する場合、銅箔を薄肉化した方がより高容量の電池を得ることができる。そのような観点から、典型的には２〜５０μｍ、より典型的には５〜２０μｍ程度である。 There is no restriction | limiting in particular in the thickness of copper foil, What is necessary is just to select suitably according to a required characteristic. Generally, the thickness is 1 to 100 μm, but when used as a current collector for a negative electrode of a lithium secondary battery, a battery having a higher capacity can be obtained by thinning the copper foil. From such a viewpoint, it is typically 2 to 50 μm, more typically about 5 to 20 μm.
２．シランカップリング処理
シランカップリング処理は、銅箔の上下面のうち負極活物質との密着性が要求される少なくとも一面にシランカップリング剤を浸漬、塗布及び噴霧などによって接触させ、その後、乾燥時の熱によりシランカップリング剤を銅箔表面の銅と反応させ、銅箔表面に固定することで行う事ができる。シランカップリング剤は銅箔と負極活物質の間の接着剤としての役割のほか、防錆性を高める役割も果たす。
2. Silane coupling treatment The silane coupling treatment is performed by bringing a silane coupling agent into contact with at least one surface of the upper and lower surfaces of the copper foil, which requires adhesion to the negative electrode active material, by dipping, coating, spraying, etc., and then drying. This can be done by reacting the silane coupling agent with copper on the surface of the copper foil and fixing it to the surface of the copper foil. The silane coupling agent not only serves as an adhesive between the copper foil and the negative electrode active material, but also serves to enhance rust prevention.
シランカップリング剤は分子内に有機材料と反応結合する官能基、及び無機材料と反応結合する官能基を同時に有する有機ケイ素化合物である。有機材料と反応結合する官能基としては、例えば、ビニル基、エポキシ基、スチリル基、アクリロキシ基、メタクリロキシ基、アミノ基、Ｎ−フェニルアミノプロピル基、ウレイド基、クロロプロピル基、メルカプト基、イソシアネート基、スルフィド基、ヘキシル基、イミダゾール基等が挙げられ、アミノ基、ビニル基、エポキシ基、ヘキシル基が好ましい。無機材料と反応結合する官能基としては、例えば、クロル基等のハロゲン基、アルコキシ基、アセトキシ基、イソプロペノキシ基等が挙げられる。シランカップリング剤は２種以上を組み合わせて用いることもできる。 A silane coupling agent is an organosilicon compound having simultaneously a functional group reactively bonded to an organic material and a functional group reactively bonded to an inorganic material in the molecule. Examples of functional groups reactively bonded to organic materials include vinyl groups, epoxy groups, styryl groups, acryloxy groups, methacryloxy groups, amino groups, N-phenylaminopropyl groups, ureido groups, chloropropyl groups, mercapto groups, and isocyanate groups. , A sulfide group, a hexyl group, an imidazole group, and the like, and an amino group, a vinyl group, an epoxy group, and a hexyl group are preferable. Examples of the functional group reactively bonded to the inorganic material include a halogen group such as a chloro group, an alkoxy group, an acetoxy group, and an isopropenoxy group. Two or more silane coupling agents can be used in combination.
シランカップリング剤の具体例としては、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ−（ビニルベンジル）−２−アミノエチル−３−アミノプロピル、トリメトキシシラン、Ｎ−（ｐ−ビニルベンジル）−Ｎ−（トリメトキシシリルプロピル）エチレンジアミン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、ビス（３−（トリエトキシシリル）プロピル）ジスルフィド、ビス（３−（トリエトキシシリル）プロピル）テトラスルフィド、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリクロルシラン、アリルトリメトキシシラン、ジアリルジメチルシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、Ｎ−（１，３−ジメチルブチリデン）−３−アミノプロピルトリエトキシシラン、ｐ−スチリルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−クロロプロピルトリメトキシシラン、及び３−イソシアネートプロピルトリエトキシシランが挙げられる。 Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl). ) -3-Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl -3-aminopropyl, trimethoxysilane, N- (p-vinylbenzyl) -N- (trimethoxysilylpropyl) ethylenediamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-g Sidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, Vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrichlorosilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyl Limethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, p- Examples include styryltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
本発明で使用することのできるシランカップリング剤としては、特開平６−２５６３５８号公報に記載のアゾール系化合物とエポキシシラン系化合物との反応で得られたシランカップリング剤も例示することができ、その全内容を本明細書に援用する。
エポキシシラン系化合物としては、以下の一般式：
で示されるエポキシシランカップリング剤（例えば３−グリシドキシプロピルトリメトキシシラン）が特に好ましい。アゾール系化合物としては、ベンゾイミダゾール、イミダゾールが特に好ましい。アゾール系化合物とエポキシシラン系化合物との反応は、特開平６−２５６３５８号公報に説示されている条件で行うことができる。例えば、８０〜２００℃でアゾール系化合物１モルに対して０．１〜１０モルのエポキシシラン系化合物を滴下して５分〜２時間反応させる。その際、溶媒は特に不要であるが、クロロホルム、ジオキサン、メタノール、エタノール等の有機溶媒を用いてもよい。
Examples of the silane coupling agent that can be used in the present invention include silane coupling agents obtained by the reaction of an azole compound and an epoxy silane compound described in JP-A-6-256358. The entire contents of which are incorporated herein by reference.
Epoxysilane compounds include the following general formula:
An epoxy silane coupling agent represented by (for example, 3-glycidoxypropyltrimethoxysilane) is particularly preferable. As the azole compound, benzimidazole and imidazole are particularly preferable. The reaction between the azole compound and the epoxysilane compound can be performed under the conditions described in JP-A-6-256358. For example, at 80 to 200 ° C., 0.1 to 10 mol of an epoxysilane compound is added dropwise to 1 mol of an azole compound and reacted for 5 minutes to 2 hours. At that time, a solvent is not particularly required, but an organic solvent such as chloroform, dioxane, methanol, ethanol or the like may be used.
従来は、負極活物質との密着性や防錆性を上げるという目的でシランカップリング剤の有機皮膜を銅箔表面に形成することを考えていたため、シランカップリング剤の有機皮膜を銅箔表面にある程度厚く形成していた。一方、超音波溶接性については、従来、溶接エネルギーを大きく与えていたため大きな問題とはなっていなかったが、溶接エネルギーを大きく与えると溶接に使われる消耗品の消耗が激しいことから、近年のコスト削減において溶接エネルギーを小さくしても溶接性のよい銅箔が求められるようになってきた。有機皮膜は厚くなるほど銅箔の超音波溶接性が低下してしまい、超音波溶接性がもっとも良いのはシランカップリング剤が塗布される前の状態のときであるが、有機皮膜の厚みを極端に薄くすると密着性、防錆性、特には防錆性を低下させるため、超音波溶接性との両立は図ることは難しかった。そこで、本発明では密着性、防錆性及び超音波溶接性の共存を図るための適正な有機皮膜の厚みにする（従来よりも薄くする）ことで超音波溶接性とのバランスを図ることとした。 Conventionally, the organic film of the silane coupling agent was considered to be formed on the surface of the copper foil for the purpose of improving the adhesion with the negative electrode active material and the rust prevention property. To a certain extent thick. On the other hand, ultrasonic weldability has not been a big problem since a large amount of welding energy has been applied in the past. Even when the welding energy is reduced in the reduction, a copper foil having good weldability has been demanded. The thicker the organic film, the lower the ultrasonic weldability of the copper foil. The best ultrasonic weldability is in the state before the silane coupling agent is applied. If the thickness is too thin, adhesion and rust prevention properties, particularly rust prevention properties, are deteriorated, so it is difficult to achieve compatibility with ultrasonic weldability. Therefore, in the present invention, the balance with ultrasonic weldability is achieved by making the thickness of the organic film appropriate for coexistence of adhesion, rust prevention and ultrasonic weldability (thinner than conventional). did.
従って、本発明に係る銅箔の一実施形態においては、シランカップリング処理により表面に形成された有機皮膜の平均厚みＤ0が１．０〜５．０ｎｍである。有機皮膜の平均厚みは密着性、防錆性及び超音波溶接性の共存を図る観点から１．５〜４．５ｎｍが好ましく、２．０〜４．０ｎｍがより好ましい。 Therefore, in one embodiment of the copper foil according to the present invention, the average thickness D 0 of the organic film formed on the surface by the silane coupling treatment is 1.0 to 5.0 nm. The average thickness of the organic film is preferably 1.5 to 4.5 nm, more preferably 2.0 to 4.0 nm from the viewpoint of coexistence of adhesion, rust prevention, and ultrasonic weldability.
さらに、銅箔表面に残存する未反応のシランカップリング剤の割合を制御することで活物質塗付工程前の密着性、防錆性、特には防錆性を同じ塗布濃度でも向上させることを見出した。これにより、有機皮膜の平均厚みが薄くても、密着性、防錆性及び超音波溶接性のバランスが安定的に保たれる。これは、未反応のシランカップリング剤は銅との結合が弱く、水への浸漬や洗浄等により、未反応のシランカップリング剤が落ちてその部分の有機皮膜が薄くなるためでありその結果、その部分の密着性や防錆性が落ちてしまう。なお、従来は有機皮膜が十分厚いため、多少の落ちは問題とはならなかったのである。
このような負極活物質との密着性にほとんど寄与せず、特性向上に寄与しない銅と未反応の有機皮膜の厚みが厚くなるのは超音波溶接性の劣化につながるだけである。同じ膜厚であれば、銅箔表面に残存する未反応のシランカップリング剤が少ない方が密着性は向上する。
Furthermore, by controlling the ratio of the unreacted silane coupling agent remaining on the copper foil surface, it is possible to improve adhesion, rust prevention, especially rust prevention, even at the same coating concentration before the active material coating step. I found it. Thereby, even if the average thickness of an organic membrane | film | coat is thin, the balance of adhesiveness, rust prevention property, and ultrasonic weldability is maintained stably. This is because the unreacted silane coupling agent has a weak bond with copper and the unreacted silane coupling agent is dropped by water immersion or washing, and the organic film in that portion becomes thin. The adhesion and rust prevention of the part will fall. Conventionally, since the organic film is sufficiently thick, a slight drop has not been a problem.
Increasing the thickness of copper and the unreacted organic film, which hardly contributes to adhesion with such a negative electrode active material and does not contribute to improvement of characteristics, only leads to deterioration of ultrasonic weldability. If the film thickness is the same, the adhesion is improved when the amount of unreacted silane coupling agent remaining on the copper foil surface is smaller.
銅表面上の有機皮膜の厚みが一定の場合には、銅箔表面に残存する未反応のシランカップリング剤が少ない方が、防錆性の向上にもつながる。銅表面上の未反応シランカップリング剤は乾燥時に銅表面とシランカップリング剤の結合が強固になる、あるいは、脱水縮合反応が進むことで、強固なシロキサンネットワークができることで、高い防錆性が得られるようになる。未反応のシランカップリング剤が残存すると、腐食環境下に置かれたときに腐食性成分が銅箔表面に接近しやすくなり、銅箔表面の未反応の銅に対して腐食性成分が攻撃することで、銅の腐食反応が進行する。 When the thickness of the organic film on the copper surface is constant, the smaller the amount of unreacted silane coupling agent remaining on the copper foil surface, the better the rust prevention. The unreacted silane coupling agent on the copper surface has a high rust prevention property because the bond between the copper surface and the silane coupling agent becomes stronger during drying, or a strong siloxane network is formed by the progress of dehydration condensation reaction. It will be obtained. When the unreacted silane coupling agent remains, the corrosive component easily approaches the copper foil surface when placed in a corrosive environment, and the corrosive component attacks the unreacted copper on the copper foil surface. As a result, the corrosion reaction of copper proceeds.
銅箔表面に残存する未反応のシランカップリング剤の割合は、シランカップリング処理後の銅箔に対して純水に１０秒間浸漬する洗浄操作を行い、洗浄前後の有機皮膜の平均厚みを比較することで評価することが可能である。ここで使用する純水は、厳密な意味での純水である必要はなく、比抵抗２×１０5Ωｃｍ程度の蒸留水で足りる。未反応のシランカップリング剤は、銅箔表面との結合力が弱いので洗浄操作によって洗い流されてしまう。一方、シランカップリング剤が銅箔表面に十分に反応結合している場合には、洗浄操作を行っても簡単に洗い流されない。本発明においては、洗浄操作前の有機皮膜の平均厚みＤ0に対する洗浄操作後の有機皮膜の平均厚みＤ1の比率（Ｄ1／Ｄ0）により、銅箔表面に残存する未反応シランカップリング剤の割合を評価することとした。 The ratio of the unreacted silane coupling agent remaining on the surface of the copper foil was determined by performing a cleaning operation of immersing the copper foil after the silane coupling treatment in pure water for 10 seconds, and comparing the average thickness of the organic film before and after the cleaning. It is possible to evaluate by doing. The pure water used here does not need to be pure water in a strict sense, and distilled water having a specific resistance of about 2 × 10 5 Ωcm is sufficient. The unreacted silane coupling agent is washed away by the washing operation because of its weak binding force with the copper foil surface. On the other hand, when the silane coupling agent is sufficiently reactively bonded to the copper foil surface, it is not easily washed away even if the washing operation is performed. In the present invention, the unreacted silane coupling remaining on the copper foil surface is determined by the ratio (D 1 / D 0 ) of the average thickness D 1 of the organic film after the cleaning operation to the average thickness D 0 of the organic film before the cleaning operation. It was decided to evaluate the proportion of the agent.
従って、本発明に係る銅箔の好ましい一実施形態においては、Ｄ1／Ｄ0が０．６以上であり、Ｄ1／Ｄ0は０．７以上が好ましく、０．８以上がより好ましい。 Accordingly, in a preferred embodiment of the copper foil according to the present invention, D 1 / D 0 is 0.6 or more, and D 1 / D 0 is preferably 0.7 or more, and more preferably 0.8 or more.
Ｄ1／Ｄ0が小さいことは銅箔表面で密着性や防錆性を発揮しないシランカップリング剤が存在することを意味するので、上記のような範囲が好ましいことは間違いないが、Ｄ1／Ｄ0に関わらず、少なくともＤ1が１．０ｎｍ以上であるような銅箔であれば、所望の密着性及び防錆性は得られる。Ｄ1は好ましくは１．５ｎｍ以上であり、より好ましくは２．０ｎｍ以上である。 Since D 1 / D 0 is small means that there is a silane coupling agent that does not exhibit adhesion and rust prevention on the copper foil surface, the above range is surely preferable, but D 1 Regardless of / D 0 , if the copper foil has at least D 1 of 1.0 nm or more, desired adhesion and rust prevention can be obtained. D 1 is preferably 1.5 nm or more, and more preferably 2.0 nm or more.
本発明では、有機皮膜の平均厚みは、アルゴンスパッタとＸ線光電子分光分析装置（ＸＰＳ装置）を組み合わせて深さ方向の元素分析を行い、Ｓｉを検出し、かつＣ検出量がバックグラウンドレベルよりも大きい深さ範囲を有機皮膜の厚みとしてこれを複数箇所測定し、その平均値を有機皮膜の平均厚みとする。ＸＰＳ装置によるデプスプロファイルの例を図２に示す。 In the present invention, the average thickness of the organic film is determined by performing elemental analysis in the depth direction by combining argon sputtering and an X-ray photoelectron spectrometer (XPS device), detecting Si, and detecting C from the background level. The thickness of the organic film is measured at a plurality of locations, and the average value is defined as the average thickness of the organic film. An example of the depth profile by the XPS apparatus is shown in FIG.
シランカップリング剤はエタノールや水等の溶媒に溶かして使用することができる。酢酸等の添加によりｐＨを５前後（例：４．５〜５．５）に調整することにより溶液中で速やかに加水分解し、基材への反応性を高めることができる。一般に、シランカップリング剤の濃度を高くするとシランカップリング処理後の膜厚が厚くなり、低くすると薄くなる。０．１〜１．０質量％、好ましくは０．１〜０．８質量％、より好ましくは０．２〜０．８質量％の範囲としたシランカップリング剤溶液を使用することで、シランカップリング処理後の有機皮膜の平均厚みを上述した範囲にすることが可能である。 The silane coupling agent can be used by dissolving in a solvent such as ethanol or water. By adjusting the pH to around 5 (for example, 4.5 to 5.5) by adding acetic acid or the like, it can be rapidly hydrolyzed in the solution to increase the reactivity to the substrate. Generally, when the concentration of the silane coupling agent is increased, the film thickness after the silane coupling treatment is increased, and when the concentration is decreased, the film thickness is decreased. By using a silane coupling agent solution in the range of 0.1 to 1.0% by mass, preferably 0.1 to 0.8% by mass, more preferably 0.2 to 0.8% by mass, The average thickness of the organic film after the coupling treatment can be set in the above-described range.
銅箔表面に残存する未反応のシランカップリング剤を少なくする方法の一つとして、シランカップリング剤と銅箔表面の銅との反応率を高める方法がある。シランカップリング剤の反応率を高めるためには、シランカップリング剤を銅箔表面に接触させた後に十分に高い温度及び時間で乾燥させることが重要となる。具体的には５０℃以上、好ましくは８０℃以上、より好ましくは１００℃以上の雰囲気中で銅箔表面を乾燥させる。ただし、１５０℃を超えると保持時間と雰囲気によっては銅箔が変色し、外観不良となるため、１５０℃以下とするのが好ましい。また、あまり短時間の加熱だと反応が十分に進行しないため、加熱温度が低い場合、加熱時間は５秒以上とすべきであり、１０秒以上とするのが好ましい。ただし、高い加熱温度であまり長時間の加熱を行うと酸化によって銅箔表面が変色するので、加熱温度が高い場合、３００秒以下とするのが望ましい。 One method for reducing the amount of unreacted silane coupling agent remaining on the copper foil surface is to increase the reaction rate between the silane coupling agent and copper on the copper foil surface. In order to increase the reaction rate of the silane coupling agent, it is important that the silane coupling agent is dried at a sufficiently high temperature and time after contacting the surface of the copper foil. Specifically, the copper foil surface is dried in an atmosphere of 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher. However, if the temperature exceeds 150 ° C., the copper foil may be discolored depending on the holding time and atmosphere, resulting in poor appearance. Further, since the reaction does not proceed sufficiently when heating is performed for a very short time, when the heating temperature is low, the heating time should be 5 seconds or longer, and preferably 10 seconds or longer. However, if the heating is performed for a long time at a high heating temperature, the surface of the copper foil is discolored by oxidation. Therefore, when the heating temperature is high, it is desirable that the heating time is 300 seconds or less.
銅箔表面に残存する未反応のシランカップリング剤を少なくする別の方法の一つとして、未反応のシランカップリング剤を銅箔表面から除去する方法がある。先述したように、未反応のシランカップリング剤は特性向上に寄与しない。未反応のシランカップリング剤を除去しても密着性や防錆性にはほとんど影響がなく、逆に有機皮膜の厚みが薄くなって超音波溶接性が向上する。未反応のシランカップリング剤を銅箔表面から除去する方法としては、限定的ではないが、純水への浸漬、純水スプレーによる方法が挙げられる。ただし、未反応のシランカップリング剤を強力に除去してしまうと、銅箔に反応結合しているシランカップリング剤までも除去されるおそれがあるので、条件設定には留意する必要がある。 As another method for reducing the amount of unreacted silane coupling agent remaining on the surface of the copper foil, there is a method of removing the unreacted silane coupling agent from the surface of the copper foil. As described above, the unreacted silane coupling agent does not contribute to improving the characteristics. Even if the unreacted silane coupling agent is removed, there is almost no influence on adhesion and rust prevention, and conversely, the thickness of the organic film is reduced and the ultrasonic weldability is improved. The method for removing the unreacted silane coupling agent from the surface of the copper foil is not limited, and examples thereof include immersion in pure water and pure water spraying. However, if the unreacted silane coupling agent is strongly removed, even the silane coupling agent reactively bonded to the copper foil may be removed, so care must be taken in setting the conditions.
３．銅箔基材の表面性状
好ましい一実施形態においては、シランカップリング処理を施す前の表面性状が以下の条件を満たす。具体的には、銅箔の上下面の圧延平行方向における表面粗さについて、０．０１μｍ≦Ｒａ≦０．１０μｍを満たし、好ましくは、５μｍ≦ＲＳｍ≦２０μｍも満たす。Ｒａは粗さ曲線を中心線から折り返し、その粗さ曲線と中心線によって得られた面積を長さＬで割った値であり、ＲＳｍは粗さ曲線が平均線と交差する交点から求めた山谷−周期の間隔の平均値である。何れもＪＩＳ Ｂ０６０１：２００１に準拠して測定される。
3. Surface property of copper foil base material In preferable one Embodiment, the surface property before performing a silane coupling process satisfy | fills the following conditions. Specifically, the surface roughness in the rolling parallel direction of the upper and lower surfaces of the copper foil satisfies 0.01 μm ≦ Ra ≦ 0.10 μm, and preferably satisfies 5 μm ≦ RSm ≦ 20 μm. Ra is a value obtained by folding the roughness curve from the center line and dividing the area obtained by the roughness curve and the center line by the length L, and RSm is a mountain valley obtained from the intersection where the roughness curve intersects the average line -Average period interval. Both are measured according to JIS B0601: 2001.
表面粗さの小さい銅箔であっても、特許文献２に記載のように、表面に電解法により銅を析出させて表面を粗面化したり、エメリー紙で研磨処理したりして積極的に表面を粗くしてしまうと、Ｒａは０．１０μｍを超え、ＲＳｍは２０μｍを超えてしまう。 Even with a copper foil having a small surface roughness, as described in Patent Document 2, copper is deposited on the surface by an electrolytic method to roughen the surface, or actively treated by polishing with emery paper. If the surface is roughened, Ra exceeds 0.10 μm and RSm exceeds 20 μm.
すなわち、上記の表面性状は粗化処理した銅箔に比べて、凹凸が微細である。このような表面性状を有することで、超音波溶接性が向上する。理論によって本発明が限定されることを意図しないが、これは以下の理由が考えられる。圧延銅箔の場合、一般的な表面の粗化処理と比較して、オイルピットによる表面の凹凸は、より一層微細であり、これにより重なり合った銅箔同士の接触点が増える。接触点は、超音波溶接時に表面の酸化物や異物が除去され新生面が現れることで、新生面同士が接合するが、接触点が多いほど接合点が多くなり、超音波溶接性が向上する。また、密着性に関しては、表面の微細な凹凸によって材料の表面積が大きくなることで、シランカップリング剤と材料表面の接触面積が大きくなり、さらに、単位面積当たりの凹凸数が多くなることでの投錨効果の増大が生じ、密着性が増大する効果もある。 That is, the surface texture has fine irregularities compared to the roughened copper foil. By having such a surface property, ultrasonic weldability is improved. Although the present invention is not intended to be limited by theory, the following reasons can be considered. In the case of a rolled copper foil, the surface unevenness due to oil pits is much finer than that of a general surface roughening treatment, thereby increasing the number of contact points between overlapping copper foils. The contact points are formed by removing oxides and foreign substances on the surface during the ultrasonic welding and appearing new surfaces, and the new surfaces join together. However, the more contact points, the more joint points and the ultrasonic weldability improves. As for adhesion, the surface area of the material is increased by the fine irregularities on the surface, the contact area between the silane coupling agent and the material surface is increased, and the number of irregularities per unit area is increased. The throwing effect is increased, and there is an effect of increasing the adhesion.
０．０１μｍ≦Ｒａ≦０．１０μｍを条件としたのは、Ｒａが０．０１μｍ未満だと表面が平滑で、また、０．１０μｍを超えると微細な凹凸が少なくなることで、いずれの場合も重なり合った銅箔同士の接触点が少なくなり、溶接性が低下するためである。Ｒａは好ましくは０．０３≦Ｒａ≦０．０８であり、より好ましくは０．０４≦Ｒａ≦０．０６である。 The condition of 0.01 μm ≦ Ra ≦ 0.10 μm is that when Ra is less than 0.01 μm, the surface is smooth, and when it exceeds 0.10 μm, fine irregularities are reduced. This is because the number of contact points between the overlapping copper foils is reduced and weldability is lowered. Ra is preferably 0.03 ≦ Ra ≦ 0.08, more preferably 0.04 ≦ Ra ≦ 0.06.
ＲＳｍ≦２０μｍを条件としたのは、ＲＳｍが２０μｍを超えると、単位面積当たりの凹凸の数が少なくなり、重なり合った銅箔同士の接触点が少なくなることで、溶接性が低下するためである。好ましくはＲＳｍ≦１６μｍである。下限は特に制限はないが、５μｍ未満のＲＳｍを安定して工業的に製造することは技術的に難しいことからＲＳｍは典型的には５μｍ≦ＲＳｍであり、より典型的には８μｍ≦ＲＳｍである。 The condition of RSm ≦ 20 μm is that when RSm exceeds 20 μm, the number of irregularities per unit area decreases, and the number of contact points between overlapping copper foils decreases, resulting in a decrease in weldability. . Preferably, RSm ≦ 16 μm. The lower limit is not particularly limited, but RSm is typically 5 μm ≦ RSm, more typically 8 μm ≦ RSm because it is technically difficult to stably produce RSm of less than 5 μm industrially. is there.
別の好ましい一実施形態においては、シランカップリング処理を施す前の銅箔の表面がＲＳｍ／Ｒａ≦４００である。ＲＳｍ／Ｒａの増加は、銅箔表面の凹凸が緩やかになることを意味し、重なり合った銅箔同士が接触し難くなることで、溶接性を低下させる影響がある。したがって、ＲＳｍ／Ｒａ≦４００が好ましく、より好ましくはＲＳｍ／Ｒａ≦２００である。 In another preferred embodiment, the surface of the copper foil before the silane coupling treatment is RSm / Ra ≦ 400. An increase in RSm / Ra means that the unevenness on the surface of the copper foil becomes gentle, and the overlapped copper foils are difficult to contact with each other, which has the effect of reducing weldability. Therefore, RSm / Ra ≦ 400 is preferable, and RSm / Ra ≦ 200 is more preferable.
なお、以上の説明はシランカップリング処理を行う前の銅箔の表面性状についてであるが、本発明においてはシランカップリング処理により形成される有機皮膜の厚みが極めて薄いため、シランカップリング処理を行った後も同様の表面性状が保持される。 In addition, although the above description is about the surface property of copper foil before performing a silane coupling process, since the thickness of the organic film formed by a silane coupling process is very thin in this invention, a silane coupling process is carried out. Similar surface properties are maintained after the process.
上記のような表面性状を有する圧延銅箔は、研磨処理や電着粒のめっきといった粗化処理を行わずに、オイルピットに起因する表面の凹凸状態を制御することにより構築することが可能である。オイルピットとは、ロールバイト内で圧延用ロールと被圧延材により封じ込められた圧延油が、被圧延材の表面に部分的に発生する微細な窪みである。粗化処理を行ってしまうと、オイルピットの微細凹凸が失われてしまうため好ましくない。粗化処理工程が省略されるので、経済性・生産性が向上するメリットもある。 The rolled copper foil having the surface properties as described above can be constructed by controlling the surface unevenness caused by oil pits without performing a roughening treatment such as polishing treatment or electrodeposition grain plating. is there. The oil pit is a fine recess in which rolling oil confined by a rolling roll and a material to be rolled within a roll bite is partially generated on the surface of the material to be rolled. If the roughening treatment is performed, fine unevenness of the oil pit is lost, which is not preferable. Since the roughening process is omitted, there is also an advantage that economic efficiency and productivity are improved.
圧延銅箔のオイルピットの形状、すなわち表面性状は、圧延ロールの表面粗さ、圧延速度、圧延油の粘度、１パス当たりの圧下率（とりわけ最終パスの圧下率）などを調節する事で制御可能である。例えば、Ｒａの大きな圧延ロールを使用すれば得られる圧延銅箔のＲａも大きくなり、逆に、Ｒａの小さな圧延ロールを使用すれば得られる圧延銅箔のＲａも小さくなりやすい。また、圧延速度を速く、圧延油の粘度を高く、又は１パス当たりの圧下率を小さくすることでオイルピットの発生量が増加し、ＲＳｍが小さくなりやすい。逆に、圧延速度を遅く、圧延油の粘度を低く、又は１パス当たりの圧下率を大きくすることでオイルピットの発生量が減少し、ＲＳｍが大きくなりやすい。
一方、電解銅箔については、電流密度を調整することで所定の表面粗さＲａにすることが可能である。
The shape of the oil pit of the rolled copper foil, that is, the surface properties, is controlled by adjusting the surface roughness of the rolling roll, the rolling speed, the viscosity of the rolling oil, the rolling reduction per pass (especially the rolling reduction of the final pass), etc. Is possible. For example, if a rolling roll having a large Ra is used, Ra of the rolled copper foil obtained is also increased. Conversely, if a rolling roll having a small Ra is used, the Ra of the rolled copper foil obtained is likely to be reduced. In addition, by increasing the rolling speed, increasing the viscosity of the rolling oil, or decreasing the rolling reduction per pass, the amount of oil pits generated increases and RSm tends to decrease. Conversely, by reducing the rolling speed, lowering the viscosity of the rolling oil, or increasing the rolling reduction per pass, the amount of oil pits decreases and RSm tends to increase.
On the other hand, for the electrolytic copper foil, it is possible to obtain a predetermined surface roughness Ra by adjusting the current density.
本発明に係る銅箔を材料とする集電体とその上に形成された活物質層によって構成された負極を用いて、慣用手段によりリチウムイオン電池を作製することができる。リチウムイオン電池には、電解質中のリチウムイオンが電気伝導を担うリチウムイオン一次電池用及びリチウムイオン二次電池が含まれる。負極活物質としては、限定的ではないが、炭素、珪素、スズ、ゲルマニウム、鉛、アンチモン、アルミニウム、インジウム、リチウム、酸化スズ、チタン酸リチウム、窒化リチウム、インジウムを固溶した酸化錫、インジウム−錫合金、リチウム−アルミニウム合金、リチウム−インジウム合金等が挙げられる。 A lithium ion battery can be produced by conventional means using a negative electrode composed of a current collector made of the copper foil according to the present invention and an active material layer formed thereon. The lithium ion battery includes a lithium ion primary battery and a lithium ion secondary battery in which lithium ions in the electrolyte are responsible for electrical conduction. Examples of the negative electrode active material include, but are not limited to, carbon, silicon, tin, germanium, lead, antimony, aluminum, indium, lithium, tin oxide, lithium titanate, lithium nitride, indium-tin oxide, indium- Examples thereof include a tin alloy, a lithium-aluminum alloy, and a lithium-indium alloy.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。
例１（シランカップリング処理が特性に与える影響の検討）
［圧延銅箔の製造］
厚さ２００ｍｍ、幅６００ｍｍのタフピッチ銅のインゴットを製造し、熱間圧延により１０ｍｍまで圧延した。
次に、焼鈍と冷間圧延を繰り返し、最後に冷間圧延で、ワークロール径６０ｍｍ、ワークロール表面粗さＲａを０．０３μｍとし、最終パスの圧延速度４００ｍ／分、加工度２０％として厚さ１０μｍに仕上げた。圧延油の粘度は９．０ｃＳｔ（２５℃）であった。得られた圧延銅箔はＲａが０．１１μｍ、ＲＳｍが２９μｍ、ＲＳｍ／Ｒａが２６４であった。
EXAMPLES Examples of the present invention will be described below, but these are provided for better understanding of the present invention and are not intended to limit the present invention.
Example 1 (Examination of the effect of silane coupling treatment on properties)
[Manufacture of rolled copper foil]
A tough pitch copper ingot having a thickness of 200 mm and a width of 600 mm was manufactured and rolled to 10 mm by hot rolling.
Next, annealing and cold rolling are repeated, and finally, by cold rolling, the work roll diameter is 60 mm, the work roll surface roughness Ra is 0.03 μm, the final pass rolling speed is 400 m / min, and the workability is 20%. It finished to 10 μm. The viscosity of the rolling oil was 9.0 cSt (25 ° C.). The obtained rolled copper foil had Ra of 0.11 μm, RSm of 29 μm, and RSm / Ra of 264.
［電解銅箔の製造］
電解液として、硫酸銅（ＣｕＳＯ4・５Ｈ2Ｏ）３００ｇ／Ｌ、硫酸１２０ｇ／Ｌ、塩化物イオン濃度０．５ｍｇ／Ｌ、ニカワ濃度０．５ｍｇ／Ｌとした硫酸酸性硫酸銅溶液を用い、電解液温度約５５℃、電流密度１００Ａ／ｄｍ2で電解して１０μｍの電解銅箔を製造した。得られた電解銅箔はＲａが０．１２μｍ、ＲＳｍが１９．７μｍ、ＲＳｍ／Ｒａが１６４であった。
[Manufacture of electrolytic copper foil]
As an electrolytic solution, an acidic copper sulfate solution with copper sulfate (CuSO 4 .5H 2 O) 300 g / L, sulfuric acid 120 g / L, chloride ion concentration 0.5 mg / L, glue concentration 0.5 mg / L was used. Electrolysis was performed at an electrolyte temperature of about 55 ° C. and a current density of 100 A / dm 2 to produce an electrolytic copper foil of 10 μm. The obtained electrolytic copper foil had Ra of 0.12 μm, RSm of 19.7 μm, and RSm / Ra of 164.
［シランカップリング処理］
上記の通り製造した板厚１０μｍの圧延銅箔又は電解銅箔につき、表１に記載の濃度のＮ−（２−アミノエチル）−３−アミノプロピルトリメトキシシランに３秒間浸漬し乾燥機にて表１に記載の雰囲気温度で３分間乾燥した。その後、以下の通り、活物質の密着性、防錆性、超音波溶接性を評価した。結果を表１に示す。
[Silane coupling treatment]
The rolled copper foil or electrolytic copper foil having a thickness of 10 μm produced as described above was immersed in N- (2-aminoethyl) -3-aminopropyltrimethoxysilane having the concentration shown in Table 1 for 3 seconds in a dryer. It was dried for 3 minutes at the ambient temperature described in Table 1. Thereafter, the adhesiveness, rust prevention, and ultrasonic weldability of the active material were evaluated as follows. The results are shown in Table 1.
［活物質との密着性］
（１）平均径９μｍの人工黒鉛とポリビニリデンフルオライドを重量比１：９で混合し、これを溶剤Ｎ−メチル−２−ピロリドンに分散させる。
（２）銅箔の表面に上記の活物質を塗布する。
（３）活物質を塗布した銅箔を乾燥機にて９０℃×３０分間加熱する。なお、このときにはシランカップリング剤は銅表面にＯＨ基が結合していないため、未反応のシランカップリング剤との脱水反応により銅表面と反応することはほとんどない。
（４）乾燥後、２０ｍｍ角に切り出し、１．５トン／ｍｍ2×２０秒間の荷重をかける。
（５）上記サンプルをカッターにて碁盤目状に切り傷を形成し、市販の粘着テープ（セロテープ（登録商標））を貼り、重さ２ｋｇのローラーを置いて１往復させて粘着テープを圧着する。
（６）粘着テープを剥がし、銅箔上に残存した活物質は、表面の画像をＰＣに取り込み、二値化によって銅表面の金属光沢部分と活物質が残存する黒色部分を区別し、活物質の残存率を算出。残存率は、各サンプル３つの平均値とした。活物質密着性の判定は、残存率５０％未満を「×」、５０％以上７０％未満を「△」、７０％以上９０％未満を「○」、９０％以上を「◎」とした。
[Adhesion with active material]
(1) Artificial graphite having an average diameter of 9 μm and polyvinylidene fluoride are mixed at a weight ratio of 1: 9 and dispersed in a solvent N-methyl-2-pyrrolidone.
(2) The above active material is applied to the surface of the copper foil.
(3) The copper foil coated with the active material is heated at 90 ° C. for 30 minutes with a dryer. In this case, since the silane coupling agent has no OH group bonded to the copper surface, it hardly reacts with the copper surface due to a dehydration reaction with the unreacted silane coupling agent.
(4) After drying, cut into 20 mm squares and apply a load of 1.5 ton / mm 2 × 20 seconds.
(5) The sample is cut into a grid pattern with a cutter, a commercially available adhesive tape (Cellotape (registered trademark)) is attached, a roller with a weight of 2 kg is placed, and the adhesive tape is crimped by reciprocating once.
(6) The active material remaining on the copper foil after peeling off the adhesive tape is obtained by capturing the surface image into a PC and binarizing to distinguish between the metallic luster portion of the copper surface and the black portion where the active material remains, Calculate the survival rate. The residual rate was an average value of three samples. In the determination of the active material adhesion, a residual ratio of less than 50% was evaluated as “x”, 50% or more and less than 70% as “Δ”, 70% or more and less than 90% as “◯”, and 90% or more as “◎”.
［防錆性］
（１）銅箔を５０ｍｍ×１００ｍｍの大きさに切り出し、３枚重ね粘着テープで固定し、ビニールの袋に入れて中の空気を追い出しながらテープで封印する。
（２）試料（１）を湿潤試験機（５０℃×９０％ＲＨ）に入れ、１６８時間保持する。
（３）試料を（２）の試験機から取り出し、銅箔が重なっていた部分の表面の色調を確認する。
（４）試験後の銅箔表面の色調が試験前と同じものを「◎」、試験前と比較して、僅かに変色したものを「○」、薄い赤褐色に変色したものを「△」、表面全体が赤黒色に変色したものを「×」とした。
[Rust prevention]
(1) Cut a copper foil into a size of 50 mm × 100 mm, fix it with three layers of adhesive tape, put it in a plastic bag and seal it with tape while expelling the air inside.
(2) Place the sample (1) in a wet tester (50 ° C. × 90% RH) and hold it for 168 hours.
(3) A sample is taken out from the testing machine of (2), and the color tone of the surface of the portion where the copper foil is overlapped is confirmed.
(4) “◎” when the color tone of the copper foil surface after the test is the same as before the test, “◯” when the color tone is slightly discolored compared to before the test, “△” when the color tone is light reddish brown A sample in which the entire surface was changed to reddish black was designated as “x”.
［超音波溶接性］
（１）銅箔を１００ｍｍ×１５０ｍｍの大きさに切り出し、３０枚重ねる。
（２）ブランソン社製のアクチュエータ（型番：Ｕｌｔｒａｗｅｌｄ Ｌ２０Ｅ）にホーン（ピッチ０．８ｍｍ、高さ０．４ｍｍ）を取り付ける。アンビルは０．２ｍｍピッチを使用した。
（３）溶接条件は、圧力４０ｐｓｉ、振幅６０μｍ、振動数２０ｋＨｚ、溶接時間は０．１秒とした。
（４）上記条件で溶接した後、銅箔を１枚ずつ剥離したときに、２１枚以上の銅箔が溶接部分で破れた場合を「◎」、１１〜２０枚の銅箔が溶接部分で破れた場合を「○」、１〜１０枚の銅箔が溶接部分で破れた場合を「△」、一枚も銅箔が破れなかった場合を「×」とした。なお、銅箔を剥離する前に、ホーンに接触していた最表層の銅箔の溶接部分を実態顕微鏡にて２０倍で拡大観察し、クラックが発生していないことを確認してから剥離試験を実施した。
[Ultrasonic weldability]
(1) Cut out copper foil into a size of 100 mm × 150 mm and stack 30 sheets.
(2) A horn (pitch 0.8 mm, height 0.4 mm) is attached to a Branson actuator (model number: Ultraweld L20E). The anvil used a 0.2 mm pitch.
(3) The welding conditions were a pressure of 40 psi, an amplitude of 60 μm, a vibration frequency of 20 kHz, and a welding time of 0.1 second.
(4) After welding under the above conditions, when the copper foil is peeled one by one, the case where 21 or more copper foils are torn at the welded part is “◎”, and 11 to 20 copper foils are the welded part. The case where it was torn was designated as “◯”, the case where 1 to 10 copper foils were torn at the welded portion, “Δ”, and the case where no copper foil was torn was designated as “x”. Before peeling the copper foil, the welded portion of the outermost copper foil that was in contact with the horn was magnified 20 times with an actual microscope to confirm that there were no cracks before peeling test Carried out.
［有機皮膜の厚み］
有機皮膜の厚みは、アルゴンスパッタしながらＸＰＳ装置で銅箔の深さ方向について元素分析し、Ｓｉを検出し、かつＣ検出量がバックグラウンドレベルよりも大きな深さ範囲（ＳｉＯ2換算）を有機皮膜厚みとし、任意の５カ所の平均値を有機皮膜厚みの平均値とした。
・装置：ＸＰＳ装置（アルバックファイ社、型式５６００ＭＣ）
・真空度：５．７×１０-7Ｐａ
・Ｘ線：単色ＡｌＫα、Ｘ線出力２１０Ｗ、入射角４５°、取り出し角４５°
・イオン線：イオン種Ａｒ+、加速電圧３ｋＶ、掃引面積３ｍｍ×３ｍｍ、スパッタリングレート２．３ｎｍ／ｍｉｎ（ＳｉＯ2換算）
[Thickness of organic film]
The thickness of the organic film is measured by elemental analysis in the depth direction of the copper foil using an XPS apparatus while argon sputtering is performed, Si is detected, and the depth range where the C detection amount is larger than the background level (SiO 2 conversion) is organic. It was set as film thickness, and the average value of arbitrary five places was made into the average value of organic film thickness.
-Equipment: XPS equipment (ULVAC-PHI, Model 5600MC)
・ Degree of vacuum: 5.7 × 10 −7 Pa
X-ray: Monochromatic AlKα, X-ray output 210W, incident angle 45 °, extraction angle 45 °
Ion beam: ion species Ar + , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.3 nm / min (SiO 2 conversion)
実施例１−１〜１−９は、シランカップリング剤濃度が適当な範囲にあることで、有機皮膜厚がいずれも１．０〜５．０ｎｍの範囲にある。そのため、活物質密着性、防錆性、及び超音波溶接性のいずれも良好であった。
比較例１−１０は、シランカップリング処理未実施のため、活物質密着性及び防錆性が劣る。
比較例１−１１は、シランカップリング剤濃度が低かった。そのため、有機皮膜厚が１．０ｎｍ未満と薄く、活物質密着性及び防錆性が劣った。
比較例１−１２は、シランカップリング剤濃度が高く、有機皮膜厚が５．０ｎｍを超えており、超音波溶接性が劣った。
In Examples 1-1 to 1-9, the silane coupling agent concentration is in an appropriate range, and the organic film thickness is in the range of 1.0 to 5.0 nm. Therefore, the active material adhesion, rust prevention, and ultrasonic weldability were all good.
Since Comparative Example 1-10 is not yet subjected to the silane coupling treatment, the active material adhesion and rust prevention properties are inferior.
In Comparative Example 1-11, the silane coupling agent concentration was low. Therefore, the organic film thickness was as thin as less than 1.0 nm, and the active material adhesion and rust prevention properties were inferior.
In Comparative Example 1-12, the concentration of the silane coupling agent was high, the organic film thickness exceeded 5.0 nm, and the ultrasonic weldability was inferior.
例２（未反応のシランカップリング剤が特性に与える影響の検討）
例１と同様の方法で銅箔を製造し、活物質との密着性、防錆性、超音波溶接性を評価した。
なお、シランカップリング処理、乾燥後に、蒸留水中に１０秒間浸漬して銅箔表面を洗浄し、これを用いてＤ1を測定した。
［有機皮膜の厚み］
有機皮膜の厚みにつき、分析装置と条件は例１と同様とした。ここでの測定は、シランカップリング処理後に、蒸留水中に１０秒間浸漬して銅箔表面を洗浄する前と洗浄した後に行い、洗浄前の有機皮膜厚みの平均値をＤ0とし、洗浄後の有機皮膜厚みの平均値をＤ1とした。
Example 2 (Examination of influence of unreacted silane coupling agent on properties)
A copper foil was produced in the same manner as in Example 1, and the adhesion to the active material, rust prevention, and ultrasonic weldability were evaluated.
After the silane coupling treatment and drying, the surface of the copper foil was washed by immersing in distilled water for 10 seconds, and D 1 was measured using this.
[Thickness of organic film]
The analyzer and conditions were the same as in Example 1 for the thickness of the organic film. The measurement here is performed after the silane coupling treatment and before and after washing the surface of the copper foil by immersing in distilled water for 10 seconds, and the average value of the thickness of the organic film before washing is D 0, and after washing. the average value of the organic film thickness was D 1.
実施例２−１〜２−９は、シランカップリング剤濃度と乾燥温度が適当な範囲にあることで、有機皮膜厚がいずれも１．０〜５．０ｎｍの範囲にあり、また、Ｄ1が１．０ｎｍ以上、Ｄ1／Ｄ0が０．６以上である。そのため、活物質密着性、防錆性、及び超音波溶接性のいずれも良好であった。
比較例２−１０は、乾燥温度は適度であるものの、シランカップリング剤濃度が低かった。そのため、有機皮膜厚Ｄ0が１．０ｎｍ未満と薄く、活物質密着性及び防錆性が劣った。
比較例２−１１は、シランカップリング剤濃度が低かった。そのため、有機皮膜厚Ｄ0が１．０ｎｍ以上であっても、Ｄ1が１．０未満、Ｄ1／Ｄ0が０．６未満となり、防錆性が劣った。
比較例２−１２は、シランカップリング剤濃度が適度で有機皮膜厚Ｄ0が適当であるものの、乾燥温度が低いために未反応のシランカップリング剤が残存し、Ｄ1が１．０未満、Ｄ1／Ｄ0が０．６未満となり、防錆性が劣った。
In Examples 2-1 to 2-9, the concentration of the silane coupling agent and the drying temperature are in an appropriate range, so that the organic film thickness is in the range of 1.0 to 5.0 nm, and D 1 Is 1.0 nm or more, and D 1 / D 0 is 0.6 or more. Therefore, the active material adhesion, rust prevention, and ultrasonic weldability were all good.
In Comparative Example 2-10, the drying temperature was moderate, but the silane coupling agent concentration was low. Therefore, the organic film thickness D 0 was as thin as less than 1.0 nm, and the active material adhesion and rust prevention properties were inferior.
In Comparative Example 2-11, the concentration of the silane coupling agent was low. Therefore, even when the organic film thickness D 0 was 1.0 nm or more, D 1 was less than 1.0 and D 1 / D 0 was less than 0.6, and the antirust property was inferior.
In Comparative Example 2-12, although the silane coupling agent concentration is moderate and the organic film thickness D 0 is appropriate, the unreacted silane coupling agent remains because the drying temperature is low, and D 1 is less than 1.0. , D 1 / D 0 is less than 0.6, corrosion resistance was inferior.
例３（銅箔の表面性状が特性に与える影響についての検討）
種々の圧延銅箔及び電解銅箔について、負極活物質との密着性を評価した。
［圧延銅箔の製造］
厚さ２００ｍｍ、幅６００ｍｍのタフピッチ銅のインゴットを製造し、熱間圧延により１０ｍｍまで圧延した。次に、焼鈍と冷間圧延を繰り返し、最後に冷間圧延で、ワークロール径６０ｍｍ、ワークロール表面粗さＲａ０．０１〜０．０９μｍとし、最終パスでは圧延速度１００〜４００ｍ／分及び圧下率２０％として厚さ１０μｍに仕上げた。圧延油の粘度は９．０ｃＳｔ（２５℃）であった。
［電解銅箔の製造］
例１の電解銅箔の製造方法に対して、電流密度を調整することで表３に示す表面粗さの電解銅箔を得た。
［表面粗さ測定］
銅箔をガラス板上に乗せて固定し、レーザーテック社のコンフォーカル顕微鏡ＨＤ１００Ｄを用いて、圧延銅箔は圧延平行方向、電解銅箔は製品の長手方向の表面粗さを測定した。圧延銅箔については、上下面のうち一方の面についての測定結果を記載したが、両面とも同様の表面性状であった。Ｒａ及びＲＳｍはＪＩＳ Ｂ０６０１：２００１に準拠してレーザーテック社製ＨＤ１００Ｄを使用して測定した。
［シランカップリング処理］
上記の通り製造した板厚１０μｍの圧延銅箔及び電解銅箔を濃度０．２質量％のＮ−（２−アミノエチル）−３−アミノプロピルトリメトキシシランに３秒間浸漬した後、８０℃の温度の乾燥機内にて５分間乾燥した後、以下の通り、活物質の塗布及び密着性評価を行った。
［その他の特性］
例１と同様の方法で密着性、防錆性、有機皮膜の厚み及び超音波溶接性を評価した。
Example 3 (Examination of the effect of copper foil surface properties on properties)
About various rolled copper foil and electrolytic copper foil, the adhesiveness with a negative electrode active material was evaluated.
[Manufacture of rolled copper foil]
A tough pitch copper ingot having a thickness of 200 mm and a width of 600 mm was manufactured and rolled to 10 mm by hot rolling. Next, annealing and cold rolling are repeated, and finally, by cold rolling, the work roll diameter is 60 mm, the work roll surface roughness Ra is 0.01 to 0.09 μm, and the rolling speed is 100 to 400 m / min and the reduction rate in the final pass. 20% was finished to a thickness of 10 μm. The viscosity of the rolling oil was 9.0 cSt (25 ° C.).
[Manufacture of electrolytic copper foil]
The electrolytic copper foil having the surface roughness shown in Table 3 was obtained by adjusting the current density with respect to the method for producing the electrolytic copper foil of Example 1.
[Surface roughness measurement]
The copper foil was placed on a glass plate and fixed, and the surface roughness of the rolled copper foil in the rolling parallel direction and the electrolytic copper foil in the longitudinal direction of the product were measured using a laser tech confocal microscope HD100D. About the rolled copper foil, although the measurement result about one side was described among upper and lower surfaces, both surfaces had the same surface property. Ra and RSm were measured using HD100D manufactured by Lasertec in accordance with JIS B0601: 2001.
[Silane coupling treatment]
After immersing the rolled copper foil having a thickness of 10 μm and the electrolytic copper foil produced as described above in N- (2-aminoethyl) -3-aminopropyltrimethoxysilane having a concentration of 0.2% by mass for 3 seconds, 80 ° C. After drying for 5 minutes in a temperature drier, application of the active material and adhesion evaluation were performed as follows.
[Other characteristics]
The adhesion, rust prevention, organic film thickness and ultrasonic weldability were evaluated in the same manner as in Example 1.
結果を表３に示す。
Ｎｏ．３−１〜３−１４は、いずれもシランカップリング剤濃度と乾燥温度が適当な範囲にあることで、有機皮膜厚Ｄ0がいずれも１．０〜５．０ｎｍの範囲にあり、また、Ｄ1／Ｄ0が０．６以上であった。そのため、密着性、防錆性、及び超音波溶接性のバランスが良好であった。
また、Ｒａが０．０１〜０．１μｍの範囲にある場合、ＲＳｍが２０μｍ以下にある場合、及びＲＳｍ／Ｒａが４００以下の場合には、同程度の有機皮膜厚みであっても、特性が向上していることが分かる。具体的には、Ｎｏ．３−１はＮｏ．３−２、Ｎｏ．３−３、Ｎｏ．３−９及びＮｏ．３−１１に比べて密着性が高く、Ｎｏ．３−４はＮｏ．３−５、Ｎｏ．３−６、Ｎｏ．３−１０及びＮｏ．３−１２に比べて超音波溶接性が高い。また、Ｎｏ．３−２、Ｎｏ．３−３は、Ｎｏ．３−９、Ｎｏ．３−１１に比べ、密着性が高く、Ｎｏ．３−５、Ｎｏ．３−６は、Ｎｏ．３−１０、Ｎｏ．３−１２に比べて超音波溶接性が高い。Ｎｏ．３−７及びＮｏ．３−８はＮｏ．３−１３やＮｏ．３−１４に比べて密着性又は超音波溶接性が高い。例１と比べてもこの傾向が窺える。
No. 3-1～3-14 are all that drying temperature and the silane coupling agent concentration is in the proper range, both organic coating thickness D 0 is in the range of 1.0～5.0Nm, also, D 1 / D 0 was 0.6 or more. Therefore, the balance of adhesion, rust prevention, and ultrasonic weldability was good.
In addition, when Ra is in the range of 0.01 to 0.1 μm, when RSm is 20 μm or less, and when RSm / Ra is 400 or less, even if the organic film thickness is similar, the characteristics are It can be seen that it has improved. Specifically, no. 3-1. 3-2, no. 3-3, no. 3-9 and no. Compared to 3-11, the adhesiveness is high. 3-4 is No.3. 3-5, no. 3-6, no. 3-10 and no. Compared to 3-12, ultrasonic weldability is high. No. 3-2, no. 3-3 is No. 3-9, no. Compared with 3-11, the adhesiveness is high. 3-5, no. 3-6 is No.3. 3-10, no. Compared to 3-12, ultrasonic weldability is high. No. 3-7 and no. 3-8 is No.3. 3-13 and No.3. Compared with 3-14, adhesion or ultrasonic weldability is high. Compared to Example 1, this tendency can be seen.
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| WO2013018898A1 (en) * | 2011-08-04 | 2013-02-07 | 三井金属鉱業株式会社 | Negative-pole material manufacturing method for lithium ion secondary battery and negative-pole material for lithium ion secondary battery |
| JP5554455B1 (en) * | 2012-07-23 | 2014-07-23 | 古河電気工業株式会社 | Surface-treated copper foil and method for producing the same, electrode for lithium ion secondary battery, and lithium ion secondary battery |
| JP2014159606A (en) * | 2013-02-19 | 2014-09-04 | Hitachi Metals Ltd | Method for manufacturing aluminum foil, aluminum foil, and electrode using the same, and electricity storage device |
| WO2014178327A1 (en) * | 2013-04-30 | 2014-11-06 | 古河電気工業株式会社 | Copper foil for lithium-ion secondary battery negative electrode collector |
| JP6170516B2 (en) * | 2015-03-18 | 2017-07-26 | Ｊｘ金属株式会社 | Rolled copper foil and manufacturing method thereof, copper-clad laminate, flexible printed circuit board, and electronic device |
| CN110892561B (en) * | 2017-07-25 | 2023-04-04 | 国际壳牌研究有限公司 | Electric energy storage device |
| JP2019175802A (en) * | 2018-03-29 | 2019-10-10 | Ｊｘ金属株式会社 | Rolled copper foil for lithium ion battery current collector and lithium ion battery |
| US12027707B2 (en) | 2019-01-25 | 2024-07-02 | Shell Usa, Inc. | Electric energy storage device |
| JP6726780B1 (en) * | 2019-03-04 | 2020-07-22 | ナミックス株式会社 | Copper foil, negative electrode current collector for lithium ion battery including the same, and method for producing the same |
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| JPH07296802A (en) * | 1994-04-26 | 1995-11-10 | Sumitomo Chem Co Ltd | Manufacture of lithium secondary battery electrode, and lithium secondary battery |
| JPH09237625A (en) * | 1996-02-27 | 1997-09-09 | Dainippon Printing Co Ltd | Electrode plate for nonaqueous electrolyte secondary battery and manufacture thereof |
| JPH1021928A (en) * | 1996-06-28 | 1998-01-23 | Furukawa Circuit Foil Kk | Electrode material for secondary battery |
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2009
- 2009-07-17 JP JP2009169269A patent/JP5219952B2/en active Active
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